Synthetic resins formed by heating together a phenol-terpene resin with a phenol aldehyde resin



United SYNTHETIC RESINS ronMEn BY HEATING "ro- GETHER A PHENGL-TERPENERESIN WITH- A PHENOL ALDEHYDE RESRN JeromeBeen and Martin M. Grover,Rutherford, N. J., assignors to Rubber and Asbestos Corporation, Bloom.-field, N. J., a corporation of New Jersey No Drawing. Applicationlune 3,1952, Serial No. 291,560

9 Claims. (Cl.- 269-43) lie or rosin esters, rosin blended Withphenol-aldehyde resins, oil-soluble phenolic-aldehyde resins,polyterpenic resins and terpene-phenolic resins have been: Suggestedbecause oftheir wide compatibility with other ingredients and their lowcost. However, it has been found that.

such resins do not yield filmsof sufiicientha'rdness, durability andadhesive strength that are required for many coating and adhesiveapplications.

It has heretofore, been proposed that pre-formedphenol aldehyde resinsbe reacted with monomeric acylic terpenes to improve the physicalproperties of the resultant compounded films. Ithas also beenproposedthat phenols, aldehydes and terpenes be reacted together, orthat] phenolic-aldehyde resins be blended with terpenes for similarpurposes. However, in none of these proposals does the resulting purefilm or compounded film have sufiicient toughness and adhesion forstringent coating and adhesion requirements, such as the coating orbonding of hard non-porous surfaces.

One object of this invention is to provide novel syn; thetic resinsyielding films of high strength and, adhesiveness. A further object ofthis invention is to provide such resins which can be used as a filmreinforcer for oil modified coatings and rubber resin adhesives. A stillfurther object of this invention is to provide such resins which can beused in the preparation of high strength oleoresinous varnishes and heatset inks. Further objects and advantages of this invention willbeapparentfrorn this specification and appended claims.

In accordance with this invention it has been found, that heatingheat-hardening para-hydrocarbon substituted phenolic-aldehyde resinswith resinous reaction products of terpenic compounds and phenols yieldheat-hardening resins of high melting points, high film strength, wide,

compatibility and good solvent release. These new resins can be producedeither by heating a molten mixtureof the components or by heating thecomponents in the presence of a solvent or dispersing medium. By varyingthe specific components, the ratio of'one component to the other, and.the time and temperature of heating, a sen'esof resins is obtainedhaving a wide range of colors, melting points and solubilities. Smallquantities of resorcinol, formal= dehyde, phenol, terpenes and otherreactive monomers can be used to modify the reaction rate andsolubility.

The; heathardening para-hydrocarbon substituted phenolic aldehyde resinswhich can be usedin this invention are prepared by condensing a phenolwhose para rates ?atent F 2,741,65i Fatented Apr. 10, 1956 positioni'ss'ubstituted by a hydrocarbon group, with an excess ofmethylene-releasing compounds. Preparation of such resins has beenpreviously described in various patents including Turkington and ButlerU. S. 2,173,346. In preparing such resins suitable phenols such asp-phenyl phenol, p-t-amyl phenol, p-cyclohexyl phenol, p tertia'ryjbutyl phenol, n-butyl phenol, propyl phenol, p-hydroxydiphenol,andp-benzyl phenol are reacted in the presence of alkali with an excessof methylenereleasing agent such as formaldehyde, hexamethylenetetramine, or para-form aldehyde. The reaction is usually stopped at anintermediate stage. The resultant resins are oil soluble and are oftensubsequently neutralizedwith mild acid such as lactic acid. It isgenerally believed that the excess of methylene releasing groups in thepresence of the para substitution produces resins having short to mediummolecular chains with reactive methylol groups at their ends, and littleor no cross linkage. Heating of this resin alone is presumed to increaseitschain length and compl'exity. However, such heating renders theresin. insetuble in most aliphatic solvents, and affects its compatibility.

The-condensation products of terpenic compounds and phenols have beendescribed in various U. S. patents in cluding" Numbers-2,378,436;2,343,845; 2,471,454; 2,471,; 453; 2,475,201; 2,284,156 and 1,469,709.Preparation; of such teipene-phenolic resins is carried outby'reactin'ga phenol with terpene hydrocarbons of the CniHie series mule presence ofcatalystssuch as boron trifiuoride, hy-' drogen fluoride and substitutedsulphonic acids. Since mostterp'ene hydrocarbons as obtained innatureare tures, the probable structure of such resins consists; of shortmolecular chains of alternating terpene and phenolic groups with aterpene periodicity. These resins have also been prepared inmodifiedform by reacting a terpene, a phenol and relatively small amount ofaldehyde together,

- The resultant chain structure is presumed to be similar except that aportion of the phenolic linkages have now. been bound by the aldehydegroupings, amount of aldehyde is small such modifiedterpene phenolisresinscan be used in this invention, since there are suflicient reactivephenol components in the t'er'penehenolic resin.

Twoother types of modifications are common with terpene-phenolic resins,neither of which affect the reac-' tivityof such resins inthisinvention; One is to use. alcohol derivitives of terpen'es in reactingwith the phenol; An example is alphaterpineol. The chain structure ofthis resin is believed to be thesame as that of theterpenehydrocarbon-phenolic resin. 7

The other common modification of a terpene-phenolic resin is to modifyor extend'the resin by the addition or rosinor maleic anhydride withsubsequent'esterification ofthe rosin or anhydride. It has been foundthat the presence of such modifying ingredients'does not substan tiallyaffect the practice of this invention.

In carrying out this invention ordinary equipment canbe used, takinginto consideration the fact that the re-.. actions evolve water andgases. The preferred temper.- ature range is from about C. to 300 C.Below. about 90 C. the reaction proceeds rather slowly while above 300"C. side reactions predominate such as the heat hardening of the phenolaldehyde resin. The ratio between the" phenol-aldehyde andterpene-phenol components can be varied widely giving various mixturesof the primary reaction products, the original resins and the thermallyself-reacted phenolic-aldehyde resins. The

intermediate range, as for example three parts or the phenol aldehydecomponent to one part'of 'tei'pene phe;

nolic component, yields reaction products of wide com: patibility andsolubility. The time required for thereaction to'be completed isdependent upon the temper Where the.

ature, and presence of any modifying monomers as mentioned above and hasbeen shown to vary from about three minutes to about seventy-two hoursunder average heating conditions. Resorcinol for example increases thereaction rate but decreases the solubility in aliphatic sol- Vents.

Several specific embodiments of this invention are listed below. inthese examples the symbol TP represents terpene-phenolic resin andthesymbol HPA represents heat hardening p-hydrocarbon substituted phenolaldehyde resin.

Example ].--1OG parts of a TP resin melting at 150 C. were placed in astainless steel, steam-jacketed, positiveagitation kettle and heated to176 C. at which temperature the resin melted. 300 parts ofHPA'resin'were introduced and agitated. 'When the mass temperaturereached 150 C. a reaction took place, withthe evolution of gaseousmaterials. Upon continued application of heat during a period of 30minutes the reaction temperature reached 250 C. at which time thereaction was stopped. a

The reaction product was a dark, red, hard, brittle resin soluble inaliphatic solvents, and having a melting point in excess of 150 C. a 7

Example 2.100 parts TP resin melting at 150 C. and 300 parts HPA resinwere reacted with sufiicient resorcinol such that the ratio was TP resin(1)/I-IPA resin (3)/resorclnol (0.1). The resorcinol is used as ahardening agent.

The reaction time was minutes with a maximum reaction temperature of 175C. After reaction the mass was chilled and yielded a dark resin havingan indeterminate melting point substantially higher than that ofExample 1. This was insoluble in aliphatic solvents but soluble inaromatic solvents.-

Example 3.l200 gms. of TP resin were heated with slow stirring in analuminum beaker until fused at 157 C. 400 gms. HPA resin were then addedand the entire mass heated for minutes at a temperature between 175-210C. The reacted material was then quickly cooled. It was found to beeasily soluble in low kauributanol value solvents such as toluene. Theresultant resin was amber colored and brittle. When dissolved in toluenewith an equal amount of Neoprene AC (21 polychloroprene rubber), ityields a material which is suitable for coatings and adhesives, andforms films that are hard, tough and adherent to metallic andnon-metallic surfaces.

Neoprene solvent cements formed with the resin of Example 3 have higherbonding strength than that of either component resin as indicated below:

TABLE I Bond strength of canvas to galvanized iron Number 1 2 3 4Neoprene AC 100 100 100 100 Zinc Oxide 5 5 5 5 Magnesium Oxidem. 4 4 4 4Neozone Am; 1 1 1 l Terpene-phenolic resin. 100 O 0 0 Hydrocarbon resinD 100 0 0 Heat-hardening phenoli res 0 U 100 0 New resin 0 0 0 100Toluene 400 400 400 400 Bond strength in lbs/inch 10 13 20 30 Example4.-200 gms. of T? resin and 100 gms. of HPA resin were dissolvedtogether in Apco 467 (a chlorinated hydrocarbon solvent). The mixturewas then refluxed for 30 minutes at 215 C. The resultant resin solutionwhen used as the base of heat-set inks showed rapid solvent release,outstanding hardness and adhesion.

Example 5.--200 gms. of EPA resin and 400 gms. of TP resin were mixedfor 29 minutes at 100 C. in. a double armed dough mixer withsteam-jacket and blades. The resultant material was a hard, amber resinhaving a melting point of 176 C. and excellent solubilitycharacteristics. When formulated with a mug oil it yielded a long oilvarnish of excellent hardness, durability, adhesion and abrasionresistance. An example of such a formulation is given below:

VARNI SH RESIN One hundred pounds of the resin were cooked with 25gallons of China-wood oil at 480 F. until a 12 inch long string wasobtained. The resulting varnish was thinned to 60% solids with mineralspirits. The dry, dust-free time was /2 hour; the tack-free time was twohours and the dry-hard time was 3 /2 hours. The abrasion, water, andweather resistance of this varnish was rated as excellent and superiorto similar varnishes made from heat-hardening phenolic resins.

Example 6.Similar to Example 5 except that the time was 2 /2 hours andthe temperature 218 C. The product was insoluble in low kauri-butanolsolvent and only slightly soluble in aromatic and polar solvents. Themelting point was over 250 C., and was indeterminable.

In forming the principal reaction products of this invention it seemslikely that the reaction takes place between the reactive methylolend-groups of the phenolaldehyde resin and reactive portions of thephenol unit of the terpene-phenolic resin. The side reactions which aspreviously pointed out predominate at temperatures in excess of 300 C.or extreme excess of the phenolaldehyde resin, are presumed to be thethermal self condensations of the phenol aldehyde resin, by virtue ofthe reactive methylol end groups.

The resins prepared according to this invention and described above wereevaluated in coatings, adhesives, varnishes and heat-set inks bysubstituting them for the usual resins in standard formulations. Theproducts obtained had markedly great film strength, adhesion tononporous surfaces and solvent release. In particular a great number ofoleo-resinous varnishes and rubberresin cements and adhesives wereprepared using the products of this invention. It was found that thephysical properties were improved over formulations utilizing pheolic,polyterpenic, abietic, maleic, or terpene-phenolic resins.

In the appended claims the term terpene phenolic resin is intended toinclude the modified terpene-phenolic resins as discussed above, inaddition to the pure terpene hydrocarbon phenolic resins. The termelastorner is used as a synonym for rubber and is intended to includenatural rubbers, synthetic rubbers and other synthetic polymericmaterials which have rubbery-like properties.

We claim:

1. Resinous reaction products formed by heating together a preformedresin formed by reaction of a phenol and a terpene hydrocarbon with aheat-hardening resin formed by reaction of a para-hydrocarbonsubstituted phenol and an excess of methylene-releasing agent selectedfrom the group consisting of formaldehyde, hexamethylene tetramine, andparaformaldehyde.

2. Resinous reaction products as in claim 1 wherein said resins areheated together in the molten state.

3. A composition containing the resinous reaction product of claim 1'.

4. A solution containing a solvent, a rubbery conjugated diene polymerand the resinous reaction products of claim 1.

5. High melting resinous products readily soluble in low'kauri-butanolaliphatic solvents and formed by heaing in the fused state a preformedresin formed by reaction of a phenol and a terpene hydrocarbon with apreformed heat-hardening resin formed by reaction of a para-hydrocarbonsubstituted phenol and an excess of methylene-releasing agent selectedfrom the group con sisting of formaldehyde, hexamethylene tetramine, andparaformaldehyde.

a ray-151 6. An adhesive composition containing polychloroprene and theresinous reaction products of claim 1.

7. Resinous reaction products formed by heating together in the presenceof a solvent a preformed resin formed by reaction of a phenol and aterpene hydrocabon with a preformed heat-hardening resin formed byreaction of a para-hydrocarbon substituted phenol and an excess ofmethylene-releasing agent Selected from the group consisting offormaldehyde, hexamethylene tetramine and paraformaldehyde.

8. A protective coating composition containing a drying oil and aresinous reaction product formed by heating together a preformed resinformed by reaction of a phenol and a terpene hydrocarbon with apreformed heat hardening resin formed from a para-hydrocarbonsubstituted phenol and an excess of methylene-releasing agent selectedfrom the group consisting of formaldehyde, hexamethylene tetramine andpara-formaldehyde.

9. A heat set ink containing a solvent and a resinous reaction productformed by heating together a preformed resin formed by reaction of aphenol and a terpene hydrocarbon with a preformed heat hardening resinformed from a para-hydrocarbon substituted phenol and an excess ofmethylene-releasing agent selected from the group consisting offormaldehyde, hexarnethyiene tetramine and para-formaldehyde.

References Cited in the file of this patent FOREIGN PATENTS 637,262Great Britain May 17, 1950

1. RESINOUS REACTION PRODUCTS FORMED BY HEATING TOGETHER A PREFORMED RESIN FROMED BY REACTION OF A PHENOL AND A TERPENE HYDROCARBON WITH A HEAT-HARDENING RESIN FORMED BY REACTION OF A PARA-HYDROCARBON SUBSTITUTED PHENOL AND AN EXCESS OF METHYLENE-RELEASING AGENT SEAMETHYLENE TATRAMINE, AND PARAFORMALDEHYDE. 